Corrosion inhibitors for oil media

ABSTRACT

A rust-inhibiting oil composition is disclosed comprised of a mineral oil and an alkali-acid stable rust inhibitor which is represented by the formula: (R-Z-R2-O)y-R3 where R is an alkyl, alkenyl, alkaryl or alkenaryl radical; Z is oxygen or a methylene radical; y is a number from 1 to 4, R2 is AND R3 is a radical which remains when y hydroxyl groups are removed from a polyhydric alcohol anhydride. The base polyhydric alcohol anhydrides for R3 contains at least one hydroxyl group and at least four carbon atoms and the rust inhibitor contains at least one alkyl or alkenyl radical of at least eight carbon atoms. The rust inhibitor is used at levels of from 0.09 to 10 weight percent based upon the oil.

Primary Examiner-Daniel E. Wyman Assistant Examiner-W. CannonAttorney-Kenneth E. Mulford, Roger R. Horton and Ernest G. Almy I UnitedStates Patent 1 1 3,639,240 Mutchler 1 Feb. 1, 1972 [54] CORROSIONINHIBITORS FOR OIL MEDIA [57] ABSTRACT m inventor: John Powell Muichler,Wilmington. Del. A wfll-inhlbitins composition is disclosed compriwd ofa mineral oil and an alkali-acid stable rust inhibitor which is [73]Asslgnec: Atlas Chemlcal Industries, Inc., Wllmlrlgrepresented by theformma ton, Del. 22 Filed: Sept. 17,1969 u- PP 8581387 where R is analkyl. alkenyl. alkaryl or alkenaryl radical: Z is oxygen or a methyleneradical; y is a number from 1 to 1521 U.S.Cl 452/5212, 252/52 A, 252/396.LR: .2-,

[s11 1m.cl.... ..Cl0m 1/22 H OH H H H [58] Field ofSearc ..2s2/s2,s2 A,396 l l l l l -C-C-C- or CC- [56] References Cited l l l H H H H CH-lOHUNITED STATES PATENTS and R is a radical which remains when y hydroxylgroups 2,921,027 1/1960 Brennan ..252/396 X are removed from apolyhydric alcohol anhydride. The base 3,048,577 8/1962 Gaertner..252/52 X polyhydric alcohol anhydrides for R contains at least 1hydroxyl group and at least 4 carbon atoms and the rust inhibitorcontains at least one alkyl or alkenyl radical of at least 8 carbonatoms. The rust inhibitor is used at levels of I from .09 to 10 weightpercent based upon the oil.

6 Claims, No Drawings This invention concerns improved oil compositions.More particularly, this invention concerns oil compositions whichcontain improved rust-inhibiting agents for ferrous containing metalsurfaces.

The addition of various additives and agents to oils to enhance theirproperties and stop the loss of oil effectiveness is old in the art.These agents perform many functions some of which are: variation of oilviscosity, and prevention of oil oxidation, oil sediment buildup,corrosion, rust, and binding of moving parts, (see Lubricant Additivesby C. V. Sinalheer et al., the Lubrizol Corporation, 1967, Library ofCongress Catalogue Card No. 67-19868). ln uses where the oil is incontact with iron or iron-containing surfaces it has been found thatantirust agents or inhibitors are needed to prevent moisture attack ofthe metal surface. Among the known addi- 'tives aret he salts of fattyamines fatty imidazoles, and fatty acids; the former have poor alkalistability and the latter have poor acid stability making the choice ofadditives dependent on the oil use. Thus an unexpected change in the pHof the system leads to undesirable rusting of the metal surfaces due tosaid instabilities. The rust inhibitors of this invention are stable inboth acid and alkaline oils and in fact are not adversely effected bythe presence of either strong acids or bases.

lt is an object of this invention to provide stable oil compositionscontaining rust inhibitors.

It is another object of this invention to provide oil compositionscontaining rust inhibitors that are not affected by acid or alkalineconditions.

These objects and still further objects will become apparent to thoseskilled in the art from the following detailed description of theinvention.

The oil compositions of this invention contain a mineral oil incombination with antioxidants, detergents and other additives mentionedabove and an alkali-acid stable rust inhibitor. Said alkali-acid stablerust inhibitors can be represented by the formula:

wherein R is an alkyl, alkenyl, alkaryl or alkenaryl radical, y is anumber from 1 to 4, Z is oxygen or a methylene radical,

R is a radical which remains when y hydroxyl groups are removed from apolyhydric alcohol anhydride. Said polyhydric alcohol anhydrides containat least four carbon atoms and at least one hydroxyl group and in saidformula the radical comprised of R-ZR contains a saturated orethylenically unsaturated aliphatic hydrocarbon chain of at least eightcarbon atoms.

A detailed description of preparing the above compounds and examples ofthe classes of radicals can be found in a copending application of A. H.Sherman and J. D. Zech entitled FA TTY ETHERS OF POL YHYDRIC ALCOHOLSfiled of even date with this application. Said application and havingthe Ser. No. 858,88l is hereby incorporated by reference and pertinentportions of same are as follows:

This invention concerns novel ether compositions and a process forproducing same. More particularly, this invention concerns ethers oflipophilic epoxides, and polyhydric alcohols and their anhydrides and aprocess for producing same.

It is an object of this invention to provide novel ether compounds.

It is another object of this invention to provide a process for thepreparation of said ethers.

It is also an object of this invention to provide new surfactantcompositions which are acid and alkali stable.

"Still further objects will become apparent to those skilled in the artfrom the following detailed description of said invention.

The novel ether compositions of this invention may be represented by theformula l) [R-XR -O],-R;., and mixtures of same with compoundsrepresented by formula (2) [RX-R O],,--R,, wherein R is an alkyl,alkenyl. alkaryl. or alkenaryl radical; X is either oxygen, sulfur or amethylene radical, R is selected from a group of radicals represented bythe formulas:

y is a number from I to 4, and R is a radical remaining when y hydroxylgroups are removed from an anhydrized polyhydric alcohol, saidanhydrized polyhydric alcohol containing at least one hydroxyl group andat least four carbon atoms, R is a radical remaining when y hydroxylgroups are removed from a polyhydric alcohol which contains at leastthree hydroxyl groups and at least three carbon atoms, said mixturescontain at least 10 weight percent of compound within formula (1), andcontain no more than 10 weight percent of three carbon atom alcohols.

More particularly, the compounds of this invention, as represented byformula 1) above, will have an alkyl or alkenyl radical comprising acombination of R, X and R which is at least about eight carbon atomslong. Thus where R is an alkaryl or alkenaryl radical the alkyl oralkenyl moiety of said radicals contain a saturated or ethylenicallyunsaturated aliphatic hydrocarbon chain of at least eight carbon atoms.

Exemplary of the R radicals are the following: dodecyl, octyl, octenyl,nonylphenyl, nonenylphenyl, octadecyl, docosyl, docosenyl,octadecylphenyl, eicosyl, decyl, tetradecyl, octylphenyl, and docosenylphenyl.

In a preferred class of R radicals, the total alkyl or alkenyl chainwould be from about l0 to about 25 carbon atoms such as dodecyl andoctadecylphenyl.

Said anhydrized polyhydric alcohols are anhydrized alkanetriols,alkanetetrols, alkanepentols, hexitols, and oxyalkylene substitutedanhydrized polyhydric alcohols of the above classes, wherein theoxyalkylene content is from I to 30 mols per mol of said anhydrizedpolyhydric alcohol.

Examples of the above anhydrized polyhydric alcohols include erythritan,threitan, xylitan, sorbitan, mannitan, iditan, isosorbide,2,5-bis(hydroxymethyl) tetrahydrofuran, polyoxyethylene(l0)dulcitan,polyoxyethylene(20)xylitan, polyoxypropylene( 6)sorbitan, andpolyoxyethylene( 3 )isosorbide.

Said polyhydric alcohols are selected from alkanetetrols, alkanetriols,alkanepentols, hexitols, hexitans, pentitans, and mixtures thereof, andoxyalkylene substituted polyhydric alcohols of the above classes whereinthe oxyalkylene content is from 1 to 30 mols per mol of said polyhydricalcohol.

Examples of these polyhydric alcohols include: glycerine,l,2,3-butanetriol, erythritol, xylitol, sorbitol, l,2,5,6-hexanetetrol,threitol, 1,2,4-butanetriol, l,2,5-pentanetriol,polyoxyethylene(2)mannitol, polyoxypropylene( l0)xylitol.

A preferred class of said polyhydric alcohols and said anhydrizedpolyhydric alcohols contains at most about 10 carbon atoms.

The classes of compounds within formula (1) include 2- hydroxyalkylethers of said anhydrized polyhydric alcohols; lhydroxylmethyl alkylethers of said anhydrized polyhydric alcohols; 2-hydroxyalkenyl andl-hydroxymethylalkenylethers of said anhydrized polyhydric alcohols;alkylphenyloxyhydroxypropyl and alkenylphenyloxyhydroxypropyl ethers ofsaid anhydrized polyhydric alcohols; alkyloxyhydroxypropyl,alkenyloxyhydroxypropyl, and alkylthiohydroxypropyl,alkenylthiohydroxypropyl, alkylphenylthiohydroxypropyl andalkenylphenylthiohydroxypropyl polyhydric alcohols.

Some specific examples of such compounds include: 2- hydroxydodecylether of 1,4-sorbitan; l-hydroxymethyl) heptadecenyl ether ofpolyoxyethylene( l)xylitan; 2 hydroxy dodecyl ether of A-Polyolanhydride [A-Polyols are particular mixtures of polyhydric alcohols thepreparation of which are described in examples AE, infra,];octyloxyhydroxypropyl ether of mannitan; decenyloxyhydroxypropyl etherof isosorbide; dodecyloxyhydroxypropyl ether of isomannide; docosylphenyloxyhydroxypropyl ether of A-Polyol; octylthio(hydroxypropyl) etherof sorbitan, docosenylthio(hydroxypropyl) ether of polyoxyethyl(l0)mannitan; nonylphenylthio(hydroxypropyl) ether of polyoxyethylene( 25)isosorbide; di(dodecyloxyhydroxypropyl) ether of xylitan,tetra(nonylphenylthio[hydroxypropyll) ether of sorbitan; and othercompounds within the classes encompassed by formula l "Classes ofcompounds within formula (2) above include those listed above forformula l wherein they are ethers of nonanhydrized polyhydric alcohols.Specific examples include Z-hydroxy nonyl ether of threitol,dodecylthiohydroxypropyl ether, and 2-hydroxydodecenyl ether of sucroseA-polyol.

"A preferred group of ether compositions within formulas l and (2) areethers of A-Polyol and mixtures of compositions within formulas l and(2). Examples of the compounds within the above preferred class includeB-hydroxydocosenyl ether of sucrose A-Polyol anhydride, nonylphenylether of cornstarch A-Polyol anhydride; decyloxyhydroxypropyl ether ofxylose A-Polyol anhydride; nonylthiohydroxypropyl ether of sucrose APolyol anhydride; dodecyl ether of glucose A- Polyol, an 80-20 weightpercent mixture of B-hydroxydodecyl ether of sorbitan andnonylthiohydroxypropyl ether of threitol, and a 90-10 weight percentmixture of nonylphenyl oxy(hydroxypropyl) ether of mannitol andy-hydroxymethypentadecyl ether of sorbitan.

The novel compounds of this invention may be made by reacting anepoxide, represented by the formula (3) RX- R,, with said polyhydricalcohol or said anhydrized polyhydric alcohol in the presence of acatalyst, and a solvent, at temperatures of about 60 to about 200 C.,and in a mol ration of epoxide to alcohol from about 1 to l and up toabout 4 to 1. ln formula (3) above R and X are as defined in formula land R is an oxyranylmethyl radical. The epoxide contains an alkyl oralkenyl chain of at least eight carbon atoms. Illustrative of theseepoxides are the following commercially available compounds-Nedox lll4 amixture of terminal olefin oxides whose chain length varies from ll-l4carbon atoms, Nedox l5l8a mixture of terminal olefin oxides of carbonchain length of l5-l8, stearylglycidylether, cetylglycidylether,laurylglycidylether, and nonylphenylglycidylether.

The mechanism of this reaction is a normal epoxide addition reaction.Therefore, if an epoxide of formula (3) is reacted with a hexitolanhydride, one could write the reaction as;

ethers of said anhydrized In the above formulas the reaction productillustrates the two products which may result when the epoxide ringopens; n is the number of mols of epoxide per mol of alcohol.

During the course of the reaction the temperature is not a criticalvariable. When the temperature is within the range enumerated above, 60to about 200 C., the reaction will proceed; however, the greater thetemperature the faster the reaction should proceed. At temperaturesbelow 60 C. the reaction will proceed too slowly to be practical. Whenthe temperature exceeds 200 C. there is a possibility of some product orreactant degradation. A preferred temperature is from about to about C.

The catalysts which may be used in this reaction are the usual epoxidecatalysts. These include both the acidic catalysts such as Lewis acids,and basic catalysts such as alkali metals, their hydroxides, and basicsalts, amines, and alkali alkoxides. Examples of these catalysts are:boron trifluoride, boron trifluoride etherate or the phenol or aceticacid complex thereof, sulfuric acid, p-toluenesulfonic acid, perchloricacid, aluminum trichloride, ferric chloride, fluosulfonic acid; stannicchloride, sodium. lithium, calcium and their alkoxides, triethylamine,sodium acetate, and acid clays. The usual concentration of thesecatalyst is from 0.0l to about 5.0 weight percent of the reactants,depending upon the catalyst. A more preferred range of catalystconcentration is 0.10 to 1.0 weight percent. A preferred class ofcatalysts is BF NaOH and LiOH.

Naturally the temperatures and catalyst concentration are interdependentand the higher the catalyst concentration the more rapid the reaction ata given temperature or the higher the temperature the less catalyst isneeded.

To successfully run the subject reactions it has been found that amutual solvent is almost always needed because of the incompatability ofthe hydrophilic polyhydric alcohols and the hydrophobic epoxide. Incertain instances, however, where the hydrophilicity of the alcohol isnot too great, such as with isosorbide, the epoxide will dissolve insame, and thus it acts as its own solvent. in this case, however, atleast a 1 mol excess of polyol will be required to insure a homogeneoussolution. Solvents which have been used include dioxane, diglyme, methylethyl ketone, pyridine and dimethyl formamide. Basic catalyst can beutilized in all of these solvents, however, the acid catalysts cannot beused where the solvent is an amine or a derivative of same, thuspyridine and dimethylformamide should only be used with basic catalysts.The preferred solvents for this reaction are dioxane and diglyme.

A preferred mixture of polyhydric alcohols used in this reaction is adistillation fraction of a hydrogenolysis reaction product as describedin U.S. Pat. No. 3,278,398. In said patent the preferred polyol mixtureis a particular fraction labeled second-subfraction" on the schematicflowsheet, and it is also identified as the bottoms fraction of adistillation column called the Tetritol Column. This distillationfraction is generically called A-Polyol for the purposes of thisdisclosure. A- Polyol is an intimate mixture of polyols boiling at oraround the boiling point of glycerine and at temperatures higher thanglycerine. The A-Polyol will vary slightly in composition depending uponthe starch or sugar or combination of same used in the hydrogenolysisprocess. Thus when inverted sucrose, a 50/50 mixture of fructose andglucose, undergoes hydrogenolysis and the product is fractionated by theabove patents distillation scheme, the tetritol columns bottoms streamwill contain polyols ranging from glycerine up through the variousisomers of hexitol and include some recombination products of themonosacharrides present in the feed. This product is A- Polyol ofhydrogenolytic invert sugar. In all A-Polyols the quantity of glycerinis maintained at levels below 10 weight percent of the A-Polyolcomposition and in most instances the glycerin content will not be morethan 2 weight percent.

"To illustrate the preparation of A-Polyols, the following examples arepresented:

EXAMPLE A A 60 weight percent water solution of invert sugar, in thepresence of 2.0 weight percent of a supported nickel catalyst and 1.0weight percent of calcium carbonate is heated in an autoclave at 2000p.s.i.a. and 220 C. and reacted with hydrogen for 2 hours.

The catalyst and other insoluble salts are filtered from the reactionproduct and the filtrate is distilled to remove essentially all water attemperatures of up to 230 C. and at pressures slightly higher thanatmospheric. The distillation column bottom stream is then furtherfractionated in a second column at a still temperature of 230 C., withthe top of the column maintained at l mm. of Hg absolute. All columnsused in this example are bubble tray distillation columns.

The bottoms product of the second column contains polyols which boil attemperature around or higher than the boiling point of glycerin. Thissecond column bottoms is introduced as feed in a third column (TheTetritol Column heretofore mentioned) which is maintained at a toppressure of 100 mm. Hg absolute while the bottom temperature ismaintained at 230 C. The reflux rate and vapor rate are maintained sothat the bottom stream of said tetritol column contain at most 2 percentglycerin.

This bottom stream is within the category of polyols called A-Polyolsfor purposes ofthis disclosure.

EXAMPLE B A polyol within the class of A-Polyols is prepared byfractional distillation per example A of a hydrogenolytic product ofcorn starch hydrolyzate.

EXAMPLE C A polyol within the class of A-Polyols is prepared per exampleA by fractional distillation of a hydrogenolytic product of wood sugar.

A preferred mixture of polyhydric alcohol anhydrides is an anhydrizedA-polyol. That is an A-polyol as defined above is anhydrized undereither acid or basic conditions until up to about 2 mols of water areremoved per mol of A-polyol. The anhydrization of said A-polyol may beperformed using an acid or alkali catalyst such as mineral acido andtheir acid salts, and alkali metal earths, their hydroxides, oxides andbasic salts. Examples of such catalysts are H 80 H PO HCl, NaOH, Ca(OH)KOH, NaOOC H and LiOH. This anhydrization is made notwithstanding thefact that all A-polyols contain anhydrized polyhydric alcohols.

To illustrate the preparation of these anhydrized A- polyols, thefollowing nonlimiting examples are present:

EXAMPLE D "Two hundred grams of the A-polyol prepared according toexample A are heated to 100 C. and stirred to create a homogeneous mass.To said A-polyol is added 3 ml. of 50 percent (weight volume) aqueoussodium hydroxide. This mixture is then heated to 225 C. at which pointwater and the volatiles are given off. The heating of said mixture iscontinued until 260 C. at which point 6 weight percent of the originalmixture has been volatilized of which 92 percent is water or about 0.5mols of water per mol of polyol. This anhydrized product is then cooledto room temperature.

EXAMPLE E Per example D the A-polyol prepared in example B is heated to100 C. and 6 ml. of 50 weight percent sulfuric acid is added. Themixture is heated to 160 C. and maintained at this temperature untilweight percent volatiles of which 90 percent is water, is flashed. Thewater equals about 1.6 mols of water removed per mol ofA-Polyol.

Since many ofthe epoxides used in producing the ethers of this inventionare not particularly common, the following representative examples aregiven to illustrate their preparation.

EXAMPLE F Two hundred forty-two grams (l mol) of hexadecyl alcohol isheated to about 70 C. and 2 ml. of an ether solution of BB, (45 weightpercent BF is added. To this one adds dropwise 93 grams 1 mol) ofepichlorohydrin while maintaining the temperature at 70 to 90 C. Thismixture is stirred for an additional hour within the to C. temperaturespan and then diluted with 500 ml. of dioxane and 164 grams of sodiumaluminate. This mixture is refluxed for about 8 hours and then filtered.The filtrate is a dioxane solution of hexadecyl glycidyl ether.

EXAMPLE G Per the procedure of example F, 202 grams of tridecyl alcohol, in the presence of2 ml. of 45 weight percent ether solution of BFis mixed with epichlorohydrin and then heated at 80-90 C. for 1 hour.This mixture is then diluted with 50 ml. of dioxane and 164 grams ofsodium aluminate. This solution is reacted for about 8 hours at itsreflux temperature. The product is a tridecyl glycidyl ether.

EXAMPLE H "A mixture of 202 grams of l-dodecanethiol and 102 grams ofepichlorohydrin is heated to about 80 C. To this, over a period of 1hour and while maintaining the temperature at about 90l 10 C., is added40 grams of powdered sodium hydroxide. This mixture is then vacuumstripped to remove any volatiles formed. This mixture is then cooled anddissolved in 500 ml. of benzene and filtered to remove any saltspresent. The benzene is then stripped to leave the dodecyl glycidylthioether.

EXAMPLE I A solution of 268 grams of oleyl alcohol in 50 ml. ofdioxaneis heated to about 70 C. Two ml. ofa 45 weight percent BF ether solutionare added to the oleyl and then while maintaining the oleyl solution at70-90 C. Ninety-three grams of epichlorohydrin are added. After theaddition is completed the mixture is stirred at 80-90 C. for an hour.Then 164 grams of sodium aluminate is added in portions and the mixturestirred at 80-90 C. for an additional 8 hours. Upon filtering the solidsfrom the mixture the filtrate is a solution of oleyl glycidyl ether indioxane.

EXAMPLE J Per the procedure of example H, 146 grams of l-octanethiol isreacted with 102 grams of epichlorohydrin. The resultant product isoctyl glycidyl thioether.

To better illustrate the process of this invention and to enable thoseskilled in the art to practice the subject invention the followingnonlimiting examples of the preparation of the ethers of said inventionare presented.

EXAMPLE I To a solution of 10 grams of sucrose, A-Polyol anhydride ofexample E and 4 ml. of boron trifluoride etherate in 200 ml. of dioxaneis added 1 mol of the hexadecyl glycidyl ether as a dioxane solutionprepared in example F while maintaining the temperature at -l00 C. Afterthe addition is completed the mixture is refluxed for 2 hours. Theproduct is vacuum stripped to remove the dioxane solvent and yields ahexadecyloxy-hydroxypropyl ether of sucrose A-Polyol anhydride.

EXAMPLE 2 Per the procedure ofexample l, grams of the A-Polyol anhydrideprepared in example E are reacted with 1 mol of oleyl glycidyl ether ina dioxane solvent to yield the oleyl-oxyhydroxypropyl ether of saidanhydrized A-Polyol.

EXAMPLE 3 Per the procedure of example 1, 100 grams of the A-Polyolanhydride prepared in example E is reacted with 1 mol of dodecylglycidyl thioether to yield the dodecylthiohydroxypropyl ether of saidA-Polyol anhydride.

EXAMPLE 4 One hundred sixty-four grams of sorbitan and 3.4 liters ofdimethyl sulfoxide are heated to 110 C. and stirred under nitrogen. Tothis 3 grams of powdered potassium hydroxide is added and 367 grams ofNedox 1518 olefin oxide is gradually added. The mixture is stirred andheated at 1 10 to 120 C. for 16 hours. The product is then vacuumstripped of chemical solvents and volatiles.

EXAMPLE 5 One hundred sixty-four grams of mannitan and 1,500 millitersof dimethyl formamide are stirred and heated to 120 C. Then 2 grams ofsodium hydroxide are added and 245 grams of Nedox 1518 olefin oxide isgradually added to the above. The mixture is then heated to 140 C. andmaintained at this temperature until the epoxide number (grams ofproduct equivalent to 1 mol of free epoxide) is above 30,000. Themixture is then vacuum distilled to remove the solvent.

EXAMPLE 6 One hundred sixty-four grams of 2,5-bishydroxymethytetrahydrofuran is stirred with 1,000 milliliters ofpyridine and the mixture is heated to reflux under a nitrogen blanket.To this is added 189 grams of Nedox 1114 olefin oxide dropwise andrefluxing is continued until the epoxide number is above 30,000. Theproduct is vacuum distilled to remove the solvent.

EXAMPLE 7 One hundred grams of anhydrized A-Polyol of example D with ahydroxyl number of 1,053 is dissolved in 100 milliliters of dioxane. Thesolution is heated to 95 C. and 2 milliliters of boron trifluorideetherate is added as catalyst. Then 132 grams of Nedox l 1 14 is addeddropwise over an hour period while the temperature is maintained at 95to 1 C. After the addition is completed, the reaction mixture is stirredat 108 to 1 10 C. for an additional 2 hours. The product is stripped ofsolvent to leave a residue of 229 grams ofa homogeneous red brownliquid. The hydroxyl number is 410. Partition of the product betweenethyl acetate and aqueous sodium sulfate shows only 15.8 percent freepolyol present.

EXAMPLE 8 Per the procedure of example 7, 170 grams of Nedox 18 arereacted with 100 grams of A-Polyol anhydride of example D. The productis 273 grams of a homogeneous waxy solid whose hydroxyl number is 380.Its epoxide equivalent is infinity. Partition of this product shows only13.6 percent free polyol present.

EXAMPLE 9 Per the procedure of example 7, 191 grams of stearyl glycidylether is reacted with 100 grams of A-Polyol anhydride of example E. Theproduct is a homogeneous waxy solid, whose hydroxyl number is 325 andwhose epoxide equivalent is infinity. Partition of the product showsonly 10 percent free polyol present.

EXAMPLE 10 "Six hundred sixty-two grams of polyoxyethylene( l0)so rbitanare reacted per example 6 with 367 grams Nedox 1518 olefin oxide. Theproduct is then vacuum stripped to remove solvents and volatiles.

1 EXAMPLE 11 1,246 grams of polyoxypropylene()mannitan are reacted perthe procedure of example 5 with 1 mol of dodecylphenyl glycidyl etherover a 5-hour period at a temperature of approximately 160 C. Theresultant product is vacuum distilled to remove the solvent.

EXAMPLE 12 "One hundred seventy grams of Nedox 1518 are reacted, inaccordance with example 7, with 100 grams of A-Polyol of example B. Theresultant Nedox 1518 ether of A-Polyol cornstarch hydrolyzate is thenmixed with 130 grams of the ether product of example 10 resulting in afinal composition containing 43.5 weight percent of Nedox 1518 ether ofpolyoxyethylene(10)sorbitan and 56.5 weight percent of Nedox 15 18 etherof A-Polyol of cornstarch hydrolyzate.

EXAMPLE 13 Two hundred grams of tridecyl glycidyl ether are reacted witha 20-80 weight percent mixture of erythritol and sorbitan respectivelyaccording to the procedure of example 7. The product is a mixture oftridecyl oxy(B-hydroxypropyl) ether of sorbitan tridecyloxy(B-hydroxypropyl) ether of erythritol, tridecyl oxy(a-hydroxymethylethyl) ether of sorbitan and tridecyl oxy(a-hydroxymethyl ethyl) etherof erythritol.

The epoxide-alcohol ethers of this invention have been found to beexcellent surfactant compositions. In particular they have been shown tobe more resistant to acid and alkali solutions than organic ester typesurfactants heretofore used. They can be used an antifoaming agents,emulsifiers and dispersants, the exact utility being dependent upon therelation of the hydrophobic and hydrophilic groups present in the finalproduct. Thus said ethers can be used instead of and replace theheretofore-used ester products such as sorbitan stearate acid ester,polyoxyethylene( l0)sorbitan trioleate acid ester, andpolyoxyethylene(20)sorbitol oleate acid ester.

These inhibitors can be used iii their crude form such as those preparedin the example given above from the copending application or they can bepurified. That is, the unreacted polyol may be removed by solventextraction. One usual dual solvent system used for this extraction isethyl acetate and a sodium sulfate water solution. The reaction productis mixed in this two-phase system and the unreacted polyol dissolves inthe aqueous phase whereas the rust inhibitor dissolves in the organicphase. Decanting this mixture and evaporation of the ethyl acetate willleave the purified rust inhibitor. Thus in table 1 two ethers of Nedox1518 are used at different purity levels, and both show equalrust-inhibiting properties.

The oil component of this composition can be any mineral oil compatiblewith carrying out lubricating functions in the various locations wheremetal to metal contact occurs in the art. The viscosity ranges of theoil, of the above composition, may vary anywhere from about 50 sayboltUniversal Seconds (SUS) to greater than 2,000 SUS at 100 F. The normalrange of oils would have a viscosity from about SUS at F. to about 500SUS at 100 F. The specific viscosity would naturally depend upon theservice for which the composition is designed. Therefore where ahigh-temperature diesel engine is to be lubricated an oil with a greaterviscosity would generally be used, on the other hand where thelubrication is used at low temperatures, such as in a rear axletransmission, lower viscosities are used.

Some particular oils which are used in these compositions are an SAEmineral oil wherein the viscosity range will vary from 58 to 70 SUS at210 F. and have a Society of Automotive Engineer Scale Viscosity ofabout 30 SAE. A typical SAE 30 oil has the following properties.American Petroleum Institute Specific Gravity at 60 F. of approximately24.5, a pour point of minus 5 F. maximum, a Cleveland open cupflashpoint of4 1 5 F. minimum. A viscosity range at 210 F. of 5 8 to 63SUS and a viscosity index of 50 to 60. A typical SAE 20 oil, such asSunvis 1 1, has the following properties, a viscosity at 100 F. of100-420 SUS, an AP] gravity at 60 F. of 31-33, at Cleveland open cupflashpoint of 370 F. minimum, a fire point of 420 F. minimum, a pourpoint of. 0 F. maximum, and a density of about 7.206 pounds per gallon.

Although the oil and rust inhibitor are the two major components of thecomposition other additives may be added depending upon the use and theextent of protection to the metal surfaces that the compounder desires.As indicated above the other types of additives may be used in thecomposition, examples of these additives are: detergents, antioxidants,viscosity index adjusters, corrosion inhibitors, antiwear agents,dispersants, and antifoaming agents. Examples of these types ofadditives are as follows:

l. antifoam agents which include silicones and various organiccopolymers;

2. antistain additives which are mainly used in gear oils and includepolyoxyaluminum acylates and dibenzothiazoles; antichatter additiveswhich are used to limit the noise in limited slip differentials formotor vehicles and include amide-metal dithiophosphate combinations,amine salts of azomethine combinations and amine dithiophosphatcs;

4. antinoise additives which are called antisquawk additives forautomatic transmission fluids in motor vehicles and includen-acylsarcosines and derivatives thereof, sulfurized fatty acids andesters, organophosphorus acid, fatty acid combinations and esters ofdimerized fatty acids;

5. antifouling agents such as chlorinated hydrocarbons which are usedextensively in two-stroke engines to avoid the buildup of deposits.

Some of the more common oil additives used in oils include:

detergents such as:

a. sulfonates the normal and basic salts of petroleum sulfonic andlong-chain alkyl-substituted benzene sulfonic acids, phosphonates and/orthiophosphonates;

b. phenates: the normal and basic metal salts of alkyl phenols, alkylphenol sulfides and alkyl phenol aldehyde condensation products; and

c. alkylsubstituted salicylates, the normal and basic salts oflong-chain alkyl substituted salicylic acid.

Corrosion inhibitors, those additives which protect nonferrous metalparts from attack by oxidation products in the oil. The major classes ofthese compounds are:

a. metal dithiophosphates especially zinc diorganothiophosphates, whichcan be represented by the formula wherein R is an organic radical, M isequivalent to a metal such as zinc, barium or nickel;

b. metal dithiocarbamates especially zinc dithiocarbamate.

These compounds may be described by the general formula as 2,6-tertiarybutyl-4- bis(2,6-ditertiary butylphenol), and 4,4'-thio bis(2-methyl-6-tertiary butylphenol and b. amines such as N-phenylB-naphthamine, tetramethyldiaminodiphenylmethan, onthranilic acid,phenothiazine and its alkylated derivatives. Other additives includeviscosity adjuncts such as viscosity index improvers and pour pointdepressors and extreme pres sure additives which aid the oil inpreventing destructive metal to metal contact.

The level of these various components in the oil will depend upon theresultant properties desired. Particularly, the rust inhibitors of thisinvention may be present in quantities from about 0.09 to as high as lOweight percent based upon the weight of oil. The lower limit denotes thelevel below which the antirust effect of the compound loseseffectiveness. The upper limit is merely illustrative of the largeamounts of inhibitors which are compatible with the oil. However, 10percent is an excessive amount from an economic standpoint. A preferredrange of addition of these rust inhibitors is from about 0. l 5 to about5 weight percent ofthe composition based on thc oil.

To illustrate the effectiveness ofthe above corrosion inhibitors,various compounds within formula (A) above are prepared, are dissolvedin Sunvis l l. and are tested for a corrosionand rust-inhibitingtendencies per the following procedure.

Two percent of the rust inhibitor is, by gently stirring, dissolved inan oil. A polished metal sample is then dipped in the oil containing therust inhibitor and held over live steam for varying lengths of time. Thepolished metal surfaces are intermitently checked for rust.

Table 1 below gives the test results for three additives of thisinvention prepared and tested by the above procedure and labeledexamples la, 2a and 3a. Table I also presents data for a strip ofpolished metal where the oil contained no inhibitor and is thus outsidethe invention, this data is in the final column and is not a numberedexample.

TABLE I.RUST DATA-2% RUST INHIBITOR IN SUNVIS 11 1 Ether of anhydrlzedsucro e A-Pnlvol (30.5% polyol extracted). 2 Ether of anhydrized sucroseA-Polyol (13.6% polyol extracted). 3 Ether of anhydrlzed sucroseA-Polyol (10.0% polyol extracted).

Additional examples of compositions of this invention are as follows,all of these examples are prepared by mixing the rust inhibitor into theoil until it dissolves and then the other additives. However, the orderof addition of the components is not critical.

EXAMPLE 40 Component Grams Mineral oil (viscosity of 20 to 40 SUS atZIO" F.) I00 B-hydroxy octadecyl ether of polyoxyethylcne($l sorbitan 5EXAMPLE 50 Component Grams Paraffin oil (SUS viscosity -l00 at F.) I00Docosyloxyl l-hydroxypropyl) ether ofmannitan L4 EXAMPLE 6a ComponentGrams Mineral oil (viscosity of 500 m 510 sus at 210 F.) 100Nonylphenyloxy(nt-hydroxymcthyl-ethylt ether ofpolyoxyethylenet20lerythritan 4.0

EXAMPLE 74 Component Grams Sunvis l l [0,0DodecylphenyloxytZ-hydroxypropyl) ether ofnnhydrizcd sucrose A-polyol1.5

EXAMPLE 8a Component Grams Sunvis 11 10.000 B-hydroxydocosenyl ether oferythritan I Detergent (calcium isooctylsalicylate) 502.6-ditertiary-butyl-l,4-dimethyl henol 75 EXAMPLE 9a Component GramsOil (SAE-SO) 5,000 Stearyl oxythydroxypropyll other of polyoxyethylenetl0) snrbitan 50 EXAMPLE 10a Component Grams Oil(SAE 75) I00(litdodecyloxyhydroxypropyll other of xylitun 0.5

EXAMPLE I la Oil (SAE lOO) L000 Tctrnlnonylphenyloxyt hydmxypropylllother of polyoxyprupylenetS )sorbitan l8 N-phenyl-ulpht|-nuphthylumine 9phosphorus pcntusull'ide terpenline 7 Having thus described my inventionI claim: 1. An oil composition comprising a mineral lubricating oil inlubricating amounts and a rust inhibitor for ferrous containing whereiny is a number from 1-4, R is an alkyl, alkenyl, alkaryl or alkenarylradical, Z is an oxygen atom or a methylene radiand R is a radicalremaining after y hydroxyl groups are removed from a polyhydric alcoholanhydride where the polyhydric alcohol anhydride has at least fourcarbon atoms and at least one hydroxyl group, and the radical comprisedof R-ZR contains a saturated or ethylenically unsaturated aliphatichydrocarbon chain of at least eight carbon atoms.

2. An oil composition according to claim 1 wherein said R radical is aradical remaining after from one to four hydroxyl groups are removedfrom a polyhydric alcohol anhydride selected from the group consistingof anhydrides of hexitol, pentitols, alkane tetrols, alkane pentols andpolyoxyalkylene dei'ivatives of these wherein the polyoxyalkylene chainis from one to 30 polyoxyalkylene units long.

3 An oil composition according to claim 1 wherein the alkyl or alkenylmoiety of the rust inhibitor represented 'the radical comprised of R ZRis from 10 to 25 carbon atoins lon 4. An 01% composition according toclaim 1 wherein said rust inhibitor is a mixture of fatty others andsaid R radical of the formula of claim 1 is derived from an anhydrizedpolyol mixtur ofa distillation fraction ofa hydrogenolytic product ofsugar starch or mixture of same wherein said distillation fraction' iscomprised of polyhydric alcohols which boil at or above the boilingpoint of glycerine, wherein up to 2 mols of water per mol of polyhydricalcohol has been removed.

5. An oil composition according to claim 4 wherein the alkyl or alkenylmoiety of the rust inhibitor contains from 10 to 25 carbon atoms.

6.l An oil composition according to claim 2 wherein said radicalcomprised of RZR contains a saturated or ethylenically unsaturatedaliphatic hydrocarbon chain of 10 to 25 carbon atoms.

2. An oil composition according to claim 1 wherein said R3 radical is aradical remaining after from one to four hydroxyl groups are removedfrom a polyhydric alcohol anhydride selected from the group consistingof anhydrides of hexitol, pentitols, alkane tetrols, alkane pentols andpolyoxyalkylene derivatives of these wherein the polyoxyalkylene chainis from one to 30 polyoxyalkylene units long.
 3. An oil compositionaccording to claim 1 wherein the alkyl or alkenyl moiety of the rustinhibitor represented the radical comprised of R-Z-R2- is from 10 to 25carbon atoms long.
 4. An oil composition according to claim 1 whereinsaid rust inhibitor is a mixture of fatty ethers and said R3 radical ofthe formula of claim 1 is derived from an anhydrized polyol mixture of adistillation fraction of a hydrogenolytic product of sugar, starch ormixture of same wherein said distillation fraction is comprised ofpolyhydric alcohols which boil at or above the boiling point ofglycerine, wherein up to 2 mols of water per mol of polyhydric alcoholhas been removed.
 5. An oil composition according to claim 4 wherein thealkyl or alkenyl moiety of the rust inhibitor contains from 10 to 25carbon atoms.
 6. An oil composition according to claim 2 wherein saidradical comprised of R-Z-R2- contains a saturated or ethylenicallyunsaturated aliphatic hydrocarbon chain of 10 to 25 carbon atoms.